Chasing a modest target of 199 for victory, Asia coasted to 50 without loss from just 10 overs before Pollock claimed three wickets in the 11th over to turn the match on its head.
Jacques Kallis claimed the key wickets of Kumar Sangakkara (35) and Shahid Afridi (13) with the help of perfect conditions for swing bowling.
However Abdul Razzaq (38) and Anil Kumble (24) offered late hope with a seventh wicket stand of 56 before Kallis returned to trap Kumble lbw.
The drama, however, was just beginning. Zaheer Khan marshalled his fellow bowlers towards the target with an unbeaten 20. Shoaib Akhtar smashed Justin Kemp for a straight six to bring the target down to just five runs needed with two and a half overs remaining.
Shoaib was given out next ball when he squeezed a yorker to backward point where Justin Ontong held the catch.
With just three runs required from the final two overs, and number 11 Ashish Nehra on strike, South African fast bowler Dale Steyn produced the perfect yorker to uproot middle stump.
Earlier Ashwell Prince held the African innings together with an unbeaten 78 after the home side had lost the toss and crashed to 57-5 in the face of quality swing bowling from Indian left armer Zaheer Khan (3-37).
Prince faced 113 deliveries and struck just five boundaries during a cautious but crucial innings that kept Africa in the match. He added 84 with Mark Boucher (42) for the sixth wicket just as the match appeared to be heading for an early finish.
SCOREBOARD
AFRICA XI:
A.B. de Villiers lbw b Shoaib 24
H.H. Dippenaar c Sehwag b Zaheer 14
J.H. Kallis c Nehra b Zaheer 4
J.L. Ontong lbw b Zaheer 0
A.G. Prince not out 78
S.O. Tikolo c Sangakkara b Nehra 0
M.V. Boucher lbw b Muralitharan 42
S.M. Pollock b Kumble 2
N. Boje c Sangakkara b Afridi 3
J.M. Kemp lbw b Shoaib 4
D.W. Steyn run out 3
EXTRAS (LB-7, W-11, NB-6) 24
Total (all out, 44.3 overs) 198
FALL OF WKTS: 1-39, 2-44, 3-44, 4-53, 5-57, 6-141, 7-152, 8-164, 9-174.
BOWLING: Shoaib Akhtar 7.3-0-40-2 (6nb); Zaheer Khan 8-0-37-3 (2w); Nehra 5-12-19-1; Abdul Razzaq 3-0-17-0 (1w); Kumble 10-0-39-1 (2w); Muralitharan 9-1-26-1 (1w); Shahid Afridi 2-0-13-1 (1w).
SUBSTITUTION: T.M. Odoyo (did not bat) by J.M. Kemp.
ASIA XI:
K.C. Sangakkara b Kallis 35
V. Sehwag c Boucher b Pollock 21
Yousuf Youhana c Boucher b Pollock 1
Mohammad Ashraful c Tikolo b Pollock 0
Inzamamul Haq c Dippenaar b Kemp 6
Shahid Afridi c Boucher b Kallis 13
Abdul Razzaq c Boucher b Boje 38
A. Kumble lbw b Kallis 24
Zaheer Khan not out 20
Shoaib Akhtar c Ontong b Kemp 15
A. Nehra b Steyn 1
EXTRAS (LB-2, W-16, NB-2) 22
TOTAL (all out, 48.1 overs) 196
FALL OF WKTS: 1-50, 2-52, 3-52, 4-59, 5-89, 6-96, 7-152, 8-169, 9-193.
BOWLING: Pollock 10-1-32-3 (3nb, 1w); Steyn 9.1-2-40-1 (5w); Kemp 9-0-40-2 (1nb, 5w); Kallis 10-2-42-3 (2w); Boje 10-1-40-1 (1w).
SUBSTITUTION: M. Muralitharan (did not bat) by Mohammad Ashraful.
RESULT: Africa XI won by two runs.
UMPIRES: B. Doctrove (West Indies) and S.J. Davis (Australia).
TV UMPIRE: K.H. Hurter (South Africa).
MATCH REFEREE: C.H. Lloyd (West Indies).
MAN-OF-THE-MATCH: Ashwell Prince.
SECOND MATCH: Durban on Saturday.
THIRD MATCH: Durban on Sunday.—Agencies